CN109456161A - A kind of method of visible light catalytic oxidation fracture carbon-carbon bond - Google Patents
A kind of method of visible light catalytic oxidation fracture carbon-carbon bond Download PDFInfo
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- CN109456161A CN109456161A CN201710794504.9A CN201710794504A CN109456161A CN 109456161 A CN109456161 A CN 109456161A CN 201710794504 A CN201710794504 A CN 201710794504A CN 109456161 A CN109456161 A CN 109456161A
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- titanium dioxide
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- vanadium
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- 238000000034 method Methods 0.000 title claims abstract description 32
- 230000003647 oxidation Effects 0.000 title claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 16
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title claims abstract description 11
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 150
- 239000000758 substrate Substances 0.000 claims abstract description 82
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 70
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 39
- 239000001301 oxygen Substances 0.000 claims abstract description 39
- 238000007789 sealing Methods 0.000 claims abstract description 35
- 239000003054 catalyst Substances 0.000 claims abstract description 32
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 28
- 239000007787 solid Substances 0.000 claims abstract description 23
- -1 aromatic carboxylic-acid compound Chemical class 0.000 claims abstract description 16
- 229920005610 lignin Polymers 0.000 claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- 150000003934 aromatic aldehydes Chemical class 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- 238000005286 illumination Methods 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 150000003624 transition metals Chemical class 0.000 claims abstract description 5
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical group CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 93
- 239000007789 gas Substances 0.000 claims description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 42
- 235000019441 ethanol Nutrition 0.000 claims description 38
- 239000002904 solvent Substances 0.000 claims description 38
- 229910052720 vanadium Inorganic materials 0.000 claims description 18
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 claims description 9
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 9
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 claims description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 8
- OMDPSZJSEZKXSY-UHFFFAOYSA-N oxygen(2-) propan-2-ol vanadium(2+) Chemical compound [O-2].[V+2].CC(C)O.CC(C)O.CC(C)O OMDPSZJSEZKXSY-UHFFFAOYSA-N 0.000 claims description 8
- FSJSYDFBTIVUFD-SUKNRPLKSA-N (z)-4-hydroxypent-3-en-2-one;oxovanadium Chemical compound [V]=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FSJSYDFBTIVUFD-SUKNRPLKSA-N 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical class ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- IBYSTTGVDIFUAY-UHFFFAOYSA-N vanadium monoxide Chemical compound [V]=O IBYSTTGVDIFUAY-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- OFRCZTMFZRZFBC-UHFFFAOYSA-N 1,2-diphenylpropane-1,3-diol Chemical compound C=1C=CC=CC=1C(CO)C(O)C1=CC=CC=C1 OFRCZTMFZRZFBC-UHFFFAOYSA-N 0.000 claims description 2
- LZGPSZXEKATVDE-UHFFFAOYSA-N 1-(4-methoxyphenyl)-2-phenylethanol Chemical compound C1=CC(OC)=CC=C1C(O)CC1=CC=CC=C1 LZGPSZXEKATVDE-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 2
- PMAHFMBORXFDDC-UHFFFAOYSA-N 1-(3,4-dimethoxyphenyl)-2-(4-methoxyphenyl)propane-1,3-diol Chemical compound C1=CC(OC)=CC=C1C(CO)C(O)C1=CC=C(OC)C(OC)=C1 PMAHFMBORXFDDC-UHFFFAOYSA-N 0.000 claims 1
- WXHBSAGAWAUWGM-UHFFFAOYSA-N 1-(3,4-dimethoxyphenyl)-2-phenylethanol Chemical compound C1=C(OC)C(OC)=CC=C1C(O)CC1=CC=CC=C1 WXHBSAGAWAUWGM-UHFFFAOYSA-N 0.000 claims 1
- 125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 claims 1
- 210000005056 cell body Anatomy 0.000 claims 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N isopropyl alcohol Natural products CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 230000003287 optical effect Effects 0.000 claims 1
- 239000013110 organic ligand Substances 0.000 claims 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
- 230000005855 radiation Effects 0.000 abstract description 4
- 230000005284 excitation Effects 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 230000009466 transformation Effects 0.000 description 31
- 238000001819 mass spectrum Methods 0.000 description 30
- 238000004128 high performance liquid chromatography Methods 0.000 description 29
- 238000010504 bond cleavage reaction Methods 0.000 description 5
- 238000005034 decoration Methods 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000036632 reaction speed Effects 0.000 description 3
- 230000008439 repair process Effects 0.000 description 3
- 230000007017 scission Effects 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- 125000003762 3,4-dimethoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C(OC([H])([H])[H])C([H])=C1* 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- HPLXJFZCZSBAAH-UHFFFAOYSA-N [V+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] Chemical compound [V+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] HPLXJFZCZSBAAH-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Natural products CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003495 polar organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000011002 quantification Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002255 enzymatic effect Effects 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/51—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition
- C07C45/511—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups
- C07C45/512—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by pyrolysis, rearrangement or decomposition involving transformation of singly bound oxygen functional groups to >C = O groups the singly bound functional group being a free hydroxyl group
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/20—Vanadium, niobium or tantalum
- B01J23/22—Vanadium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of methods of visible light catalytic oxidation fracture carbon-carbon bond.This method is photochemical catalyst using the titanium dioxide solids that Transition Metals V is modified, and using lignin β -1 class model compound as reaction substrate, under radiation of visible light excitation, Direct Catalytic Oxidation fracture carbon-carbon bond prepares aromatic aldehyde and aromatic carboxylic-acid compound.Its reaction process is as follows: a certain amount of reaction substrate and catalyst being added in quartzy Photoreactor, suitable organic solvent and magneton is added, with upper air in replacement of oxygen reaction tube, sealing sealing is placed in integrated apparatus for photoreaction and carries out illumination reaction.Reaction temperature is 5~70 DEG C, and the reaction time is 0.5~10 hour, and aromatic aldehyde and aromatic carboxylic-acid compound are obtained after reaction.This method mild condition, easy to operate, the easily separated recycling of catalyst are a kind of new methods of high-efficiency and economic for realizing carbon-carbon bond direct oxidation fracture.
Description
Technical field
The present invention relates to a kind of methods of visible light catalytic oxidation fracture carbon-carbon bond, are a kind of to be repaired using vanadium specifically
The solid titanium dioxide of decorations is catalyst, with O2For oxygen source, low temperature is by the fragrant dimer mould of lignin β -1 under visible light illumination
Type compound direct oxidation is broken carbon-carbon bond and synthesizes aromatic aldehyde compound.
Background technique
The selective oxidation fracture of C-C key is organic synthesis and the extremely important and challenging research side in conversion field
One of to.Since C-C key bond energy is high, it is difficult to activate, conventional method generally requires the catalysis of complicated metal complex and more severe
The reaction condition (Chem.Rev.2015,115,9410-9464) at quarter realizes that the selectively fracture of the C-C key under temperate condition is tool
Significant project.Lignin is that unique one kind natural aromatic polymer, rich reserves are in nature using lignin
Raw material production has the aromatics chemicals of high added value, is the biomass trans-utilization approach an of economical and efficient, meets green
The requirement of colour chemistry and current using energy source.Lignin polymers are mainly made of three kinds of phenylpropyl alcohol alkyl monomers, between monomer
Connection type be broadly divided into several classes such as β-O-4, α-O-4,4-O-5, β-1, β-β (Ind.Crops Prod., 2004,20,131-
141).Contain a large amount of C-O keys and C-C key in these connecting keys, C-C key bond energy is high, more inertia, and selectivity, which is broken C-C key, is
From the critical issue of lignin preparation high added value monomer aromatic compound.Therefore, it develops lignin under temperate condition and is broken carbon
At the catalyst system of high added value aromatic compound, trans-utilization and its depolymerization mechanism to research lignin have important bond with carbon
Meaning.
The development of novel photocatalysis technology provides more new possibility for traditional organic catalysis, can be realized temperate condition
Under the importances such as a variety of chemical conversion process, including C-H/C-O bond activation, have in biomass trans-utilization field potential
Application prospect.The energy of solar radiation is mainly distributed on visible region and infrared region, and wherein visible region accounts for solar radiation total amount
50%.Therefore development and utilization are ten with the conversion for realizing lignin under temperate condition to visible light-responded solid photocatalysts
Divide potential green approach.
Method in the invention is using lignin β -1 model compound as reaction substrate, under visible light illumination using honest and clean
Valence Transition Metals V modified titanic oxide solid photocatalysts direct oxidation can be broken C-C key in very mild conditions, close
At aromatic aldehyde or aromatic carboxylic-acid compound.The thermocatalytic method of tradition realizes that the oxidation of lignin β -1 class model compound is disconnected
Split, have some literature reports.Baker in 2013 and Hanson report uses (CuOTf)/TEMPO system to realize that its oxidation is disconnected
It splits (ACS Catal.2013,3,3111-3122), but needs that excess base is added in system, catalyst amount is larger, substrate model
Enclose narrow, and selectivity of product is low.Mariano in 2015 promotes C-by single electron transfer using photochemistry and the method for enzymatic
C bond cleavage solution (Tetrahedron 2015,71,4236-4247), conversion ratio is higher, but still obtains mix products, and is catalyzed
System is expensive.The Cu base catalyst that 2017 seminars, Nian Lichao army are coordinated using N-heterocyclic carbine realizes β -1 model compound
Selective C-C bond cleavage solution (ACS Catal.2017,7,3344-3348), but substrate universality is lower, and homogeneous catalyst is difficult
It is utilized with separating and recovering.
It is real that the invention develops a kind of solid titanium dioxide photochemical catalyst modified using visible light and cheap transition metal V
The new method of existing carbon-carbon bond oxidation scission, reaction condition is mild, and easy to operate, substrate spectrum is wide, and pyrolysis product selectivity is high, point
From simple, the conventional method that compares is more green.
Summary of the invention
Meaning of the present invention is to have invented a kind of solid photocatalysts direct oxidation modified using vanadium under visible light
It is broken the new method of carbon-carbon bond, synthesizes aromatic compounds from the lignin model compound with β -1 connection structure.The present invention
Used in solid photocatalysts it is cheap and reaction system can be easily separated, overcome traditional catalyst higher cost, reaction
The disadvantages of condition is harsh.
The technical solution adopted by the present invention are as follows:
First catalyst the preparation method comprises the following steps: (1) utilize grafting, by suitable vanadic salts (Triisopropoxyvanadium(V) oxide or acetyl
Acetone vanadyl) it is dissolved in suitable non-polar organic solvent (specially one of toluene, benzene, hexamethylene), vanadium matter in solution
Amount fraction concentration is 0.1g/L~0.6g/L, adds solid titanium dioxide and stirs 20~60h, makes organic in vanadic salts presoma
Ligand and titanium dioxide surface hydroxyl come into full contact with and replace.It is dry after being washed again with the solvent, it obtains vanadium oxygen species and repairs
The titanium dioxide solids of decorations, are named as V-TiO2-G.The mass fraction of vanadium opposite carrier is 0.2~5.0wt%, titanium dioxide kind
When class is anatase, rutile and P25, corresponding catalyst is respectively designated as V-A-TiO2-G,V-R-TiO2-G,V-P25-G.Its
Middle A indicates that Anatase, R indicate that Rutile, G indicate Grafting method, Triisopropoxyvanadium(V) oxide VTO (Vanadium
Triisopropoxide oxide) it indicates, vanadyl acetylacetonate is with VOA (Vanadium oxide acetylacetonate)
It indicates.(2) infusion process is utilized, suitable vanadic salts (one of vanadium trichloride, ammonium metavanadate, sodium metavanadate) is dissolved in ethyl alcohol
Or water, vanadium mass fraction concentration is 0.1g/L~0.6g/L in solution, adds solid titanium dioxide and stirs 20~40h, then rises
High-temperature evaporates solvent, and obtained solid is dry.Then again by this solid be warming up in air 400~550 DEG C roasting 2~
5h obtains the titanium dioxide of barium oxide modification, names V-TiO2- I, the mass fraction of vanadium opposite carrier is 0.2~
5.0wt%.When titanium dioxide type is anatase, rutile and P25, corresponding catalyst is respectively designated as V-A-TiO2-I,V-
R-TiO2-I,V-P25-I.Vanadium trichloride VT (Vanadium trichloride) expression, ammonium metavanadate AM (Ammonium
Metavanadate it) indicates, sodium metavanadate is indicated with SM (Sodium metavanadate).
This method reaction process is as follows: a certain amount of reaction substrate and catalyst being added in quartzy Photoreactor, are added
Suitable organic solvent is covered grournd glass cock and sealed, it is anti-to be placed in Integrated Light with upper air in replacement of oxygen reaction tube
It answers and carries out illumination reaction in device.Reaction temperature is 5~70 DEG C, and the reaction time is 30~600 minutes, and aromatic aldehyde is obtained after reaction
With aromatic carboxylic acids class product.
The reaction substrate is 1,2- diphenyl ethyl alcohol, 1- (4- methoxyphenyl) -2- phenylethanol, 1- (3,4- diformazan
Phenyl) -2- phenylethanol, bis- (4- methoxyphenyl) ethyl alcohol of 1,2-, 1- (3,4- Dimethoxyphenyl) -2- (4- methoxy
Base phenyl) ethyl alcohol, 1,2- diphenyl -1,3- propylene glycol, bis- (4- the methoxyphenyl) -1,3- propylene glycol of 1,2-, 1- (3,4- diformazan
Phenyl) -2- (4- methoxyphenyl) -1,3- propylene glycol one kind；The lignin model compound is in initial reaction body
Molar concentration in system is 0.02~0.15mol/L；The mass ratio that feeds intake of the catalyst and reaction substrate is 0.1~1.0；Institute
Stating overhead gas in reaction tube is oxygen, oxygen pressure 1atm；The organic solvent be acetonitrile, acetone, 1,2- dichloroethanes,
One of chloroform, N,N-dimethylformamide, ethyl acetate；The reaction speed of agitator is 200~700r/min；Reaction temperature
Degree is 5~70 DEG C, and the reaction time is 30~600 minutes.
Preferable reaction condition are as follows: molar concentration of the reaction substrate in initial reaction system is 0.04~0.10mol/
L；The mass ratio that feeds intake of the catalyst and reaction substrate is 0.3~1.0；The organic solvent is acetonitrile, acetone, 1,2- dichloro
One of ethane, chloroform；The reaction speed of agitator is 300~650r/min；The reaction temperature is 20~50 DEG C, reaction
Time is 100~500 minutes；The catalyst is modifies with Triisopropoxyvanadium(V) oxide, vanadyl acetylacetonate, vanadium trichloride forerunner
One of P25 catalyst, preferably V carrying capacity is 2~5wt%.
Most preferably are as follows: molar concentration of the reaction substrate in initial reaction system is 0.05~0.08mol/L；It is described to urge
The mass ratio that feeds intake of agent and reaction substrate is 0.4~0.8；The organic solvent is acetonitrile, in acetone, 1,2- dichloroethanes
It is a kind of；The reaction speed of agitator is 400~600r/min；The reaction temperature be 40~50 DEG C, the reaction time be 180~
420 minutes；The catalyst is the solid catalysis that grafting preparation is used using Triisopropoxyvanadium(V) oxide, vanadyl acetylacetonate as vanadium source
Agent, V carrying capacity is 3~5wt% on catalyst；
Catalyst amount increases, and the complete conversion reaction time shortens；V carrying capacity increases, increased activity, and aromatic aldehyde in product
Selectivity increases, it is contemplated that economical in reaction and mass transfer influence, concentration of substrate and catalyst feed ratio will be maintained at suitable
In the range of.
Compared with the method for existing Catalytic lignin β -1 model compound carbon-carbon bond oxidation scission, the present invention has
Following advantage:
1. catalyst is the titanium dioxide solids of transition metal modification, cheap and easy to get, preparation method is simple, can be easily separated,
Easily recycled from reaction system.
2. the solid catalyst can absorb can visible light, the radiation of visible light of low-power can provocative reaction, do not need plus
The harsh conditions such as heat.
3. reaction condition is very mild, complete conversion is can be realized in room temperature normal pressure.
Detailed description of the invention
Fig. 1 is the GC-MS analysis spectrogram of system after embodiment 1 is reacted.
Specific embodiment
In order to which the present invention will be described in further detail, several specific implementation cases are given below, but the present invention is unlimited
In these embodiments.
Catalyst specific is the preparation method comprises the following steps: (1) utilizes grafting, by suitable vanadic salts (Triisopropoxyvanadium(V) oxide or acetyl
Acetone vanadyl) it is dissolved in suitable non-polar organic solvent (specially one of toluene, benzene, hexamethylene), vanadium matter in solution
Amount fraction concentration is 0.1g/L~0.6g/L, adds solid titanium dioxide and stirs 20~60h, makes organic in vanadic salts presoma
Ligand and titanium dioxide surface hydroxyl come into full contact with and replace.It is dry after being washed again with the solvent, it obtains vanadium oxygen species and repairs
The titanium dioxide solids of decorations, are named as V-TiO2-G.The mass fraction of vanadium opposite carrier is 0.2~5.0wt%, titanium dioxide kind
When class is anatase, rutile and P25, corresponding catalyst is respectively designated as V-A-TiO2-G,V-R-TiO2-G,V-P25-G.Its
Middle A indicates that Anatase, R indicate that Rutile, G indicate Grafting method, Triisopropoxyvanadium(V) oxide VTO (Vanadium
Triisopropoxide oxide) it indicates, vanadyl acetylacetonate is with VOA (Vanadium oxide acetylacetonate)
It indicates.(2) infusion process is utilized, suitable vanadic salts (one of vanadium trichloride, ammonium metavanadate, sodium metavanadate) is dissolved in ethyl alcohol
Or water, vanadium mass fraction concentration is 0.1g/L~0.6g/L in solution, adds solid titanium dioxide and stirs 20~40h, increases
Temperature evaporates solvent, is warming up to 400~550 DEG C of 2~5h of roasting in air after obtained solid is dry, obtains barium oxide and repair
The titanium dioxide of decorations, is named as V-TiO2- I, the mass fraction of vanadium opposite carrier are 0.2~5.0wt%.Titanium dioxide type is
When anatase, rutile and P25, corresponding catalyst is respectively designated as V-A-TiO2-I,V-R-TiO2-I,V-P25-I.Tri-chlorination
Vanadium indicates that ammonium metavanadate is indicated with AM (Ammonium metavanadate), inclined vanadium with VT (Vanadium trichloride)
Sour sodium is indicated with SM (Sodium metavanadate).
Embodiment 1
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 2
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent acetone (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 3
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent 1,2- dichloroethanes (concentration of substrate 0.05mol/L) is added.Replacement of oxygen reaction tube
Interior upper air, sealing are placed in integrated apparatus for photoreaction, and revolving speed 500r/min, light source can for single wavelength 455nm's
Light-exposed LED light, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and uses efficient liquid phase
Chromatogram quantification, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 4
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent chloroform (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 5
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent ethyl acetate (concentration of substrate 0.05mol/L) is added.On in replacement of oxygen reaction tube
Square air, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible light of single wavelength 455nm
LED light, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and uses high performance liquid chromatography
Quantitative, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 6
In the quartzy light reaction pipe of 5mL, 0.02mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.02mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 7
In the quartzy light reaction pipe of 5mL, 0.08mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.08mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 8
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 0.5wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top in replacement of oxygen reaction tube
Air, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, quantitative with high performance liquid chromatography,
The substrate transformation rate and product yield are shown in Table 1.
Embodiment 9
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 2wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 10
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 5wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 11
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VOA
Amount is 0.5wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top in replacement of oxygen reaction tube
Air, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, quantitative with high performance liquid chromatography,
The substrate transformation rate and product yield are shown in Table 1.
Embodiment 12
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VOA
Amount is 2wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 13
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VOA
Amount is 5wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 14
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-I-VT
Amount is 0.5wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top in replacement of oxygen reaction tube
Air, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 15
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-I-VT
Amount is 2wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 16
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-I-VT
Amount is 5wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 17
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-I-AM
Amount is 2wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 18
In the quartzy light reaction pipe of 5mL, 0.05mmol 1,2- diphenyl ethyl alcohol, 5mg V-A-TiO is added2-G-VTO
(V carrying capacity is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.On in replacement of oxygen reaction tube
Square air, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible light of single wavelength 455nm
LED light, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and uses high performance liquid chromatography
Quantitative, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 19
In the quartzy light reaction pipe of 5mL, 0.05mmol 1,2- diphenyl ethyl alcohol, 5mg V-R-TiO is added2-G-VTO
(V carrying capacity is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.On in replacement of oxygen reaction tube
Square air, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible light of single wavelength 455nm
LED light, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and uses high performance liquid chromatography
Quantitative, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 20
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 300r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 21
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 650r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 22
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is that (> 420nm, adds 420nm to filter to xenon lamp
Piece), temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 23
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 10 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 24
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 60 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 25
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 1h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 26
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 5mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 3h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 27
In the quartzy light reaction pipe of 5mL, 0.05mmol 1 is added, 2- diphenyl ethyl alcohol, (V is carried 1mg V-P25-G-VTO
Amount is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top is empty in replacement of oxygen reaction tube
Gas, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 28
In the quartzy light reaction pipe of 5mL, 0.05mmol 1,2- diphenyl ethyl alcohol, 10mg V-P25-G-VTO (V is added
Carrying capacity is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Top in replacement of oxygen reaction tube
Air, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is the visible LED of single wavelength 455nm
Lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and fixed with high performance liquid chromatography
Amount, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 29
In the quartzy light reaction pipe of 5mL, 0.05mmol 1,2- bis- (4- methoxyphenyl) ethyl alcohol, 10mg V- is added
P25-G-VTO (V carrying capacity is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Replacement of oxygen
Upper air in reaction tube, sealing are placed in integrated apparatus for photoreaction, and revolving speed 500r/min, light source is single wavelength
The visible LED lamp of 455nm, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and
Quantitative with high performance liquid chromatography, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 30
In the quartzy light reaction pipe of 5mL, 0.05mmol 1,2- diphenyl -1,3-PD, 10mg V-P25- is added
G-VTO (V carrying capacity is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate 0.05mol/L) is added.Replacement of oxygen reaction
Upper air in managing, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/min, and light source is single wavelength 455nm's
Visible LED lamp, temperature is constant at 40 degree, reacts 6h.After reaction, gas chromatography-mass spectrum detects product, and with efficient liquid
Phase chromatogram quantification, the substrate transformation rate and product yield are shown in Table 1.
Embodiment 31
In the quartzy light reaction pipe of 5mL, 0.05mmol 1- (3,4- Dimethoxyphenyl) -2- (4- methoxybenzene is added
Base) -1,3-PD, 10mg V-P25-G-VTO (V carrying capacity is 4wt%), magneton, and 1mL solvent acetonitrile (concentration of substrate is added
For 0.05mol/L).Upper air in replacement of oxygen reaction tube, sealing are placed in integrated apparatus for photoreaction, revolving speed 500r/
Min, light source are the visible LED lamp of single wavelength 455nm, and temperature is constant at 40 degree, react 6h.After reaction, gas phase color
Spectrum-Mass Spectrometer Method product, and it is quantitative with high performance liquid chromatography, and the substrate transformation rate and product yield are shown in Table 1.
The reaction evaluating result of 1. visible light catalytic lignin β -1 model oxidation scission of table
Note:
In above-described embodiment unless otherwise indicated, quantitative approach is as follows:
Claims (9)
1. a kind of method of visible light catalytic oxidation fracture carbon-carbon bond, it is characterised in that:
Reaction substrate and catalyst are added in quartzy Photoreactor, organic solvent is added, in replacement of oxygen reaction tube
Square air, sealing sealing, be placed in apparatus for photoreaction, carry out illumination reaction under stiring, the product after reaction be aromatic aldehyde and
One or both of aromatic carboxylic-acid compound；
The reaction substrate is lignin β -1 class model compound, are as follows: 1,2- diphenyl ethyl alcohol, 1- (4- methoxyphenyl) -2-
Phenylethanol, 1- (3,4- Dimethoxyphenyl) -2- phenylethanol, bis- (4- methoxyphenyl) ethyl alcohol of 1,2-, 1- (3,4- diformazan
Phenyl) -2- (4- methoxyphenyl) ethyl alcohol, 1,2- diphenyl -1,3- propylene glycol, bis- (the 4- methoxyphenyls) -1 of 1,2-,
The one or two or more kinds of 3-propanediol, 1- (3,4- Dimethoxyphenyl) -2- (4- methoxyphenyl) -1,3- propylene glycol；
The catalyst is the titanium dioxide solids photochemical catalyst of Transition Metals V modification, and titanium dioxide is rutile-type titanium dioxide
One of titanium, anatase titanium dioxide, P25；The carrying capacity mass fraction of the vanadium is 0.1~10wt%；
The organic solvent is acetonitrile, acetone, 1,2- dichloroethanes, chloroform, N,N-dimethylformamide, one in ethyl acetate
Kind；
The light source are as follows: the single or continuous wavelength light source within the scope of 420~550nm.
2. according to the method for claim 1, it is characterised in that:
Reaction route are as follows:
The product that reaction generates is one or both of aromatic aldehyde, aromatic carboxylic-acid compound.
3. according to the method for claim 1, it is characterised in that:
Reaction temperature is 5~70 DEG C in reaction process；Reaction time is 30~600 minutes；Mixing speed is 200~700r/
min。
4. according to the method for claim 1, it is characterised in that:
Overhead gas is oxygen, oxygen pressure 1atm in the reaction tube.
5. according to the method for claim 1, it is characterised in that:
The catalysts are the titanium dioxide solids photochemical catalyst of vanadium modification, and vanadic salts presoma is Triisopropoxyvanadium(V) oxide, three
One of vanadium chloride, vanadyl acetylacetonate, ammonium metavanadate, sodium metavanadate, preferably vanadic salts presoma are isopropanol vanadyl, trichlorine
Change one of vanadium, vanadyl acetylacetonate, preferably titanium dioxide is P25；Specific preparation process is using surface graft method or leaching
Stain method: it is organic that suitable vanadic salts (Triisopropoxyvanadium(V) oxide or vanadyl acetylacetonate) is such as dissolved in suitable nonpolarity with grafting
Solvent (specially one of toluene, benzene, hexamethylene), vanadium mass fraction concentration is 0.1g/L~0.6g/L in solution, then plus
Enter solid titanium dioxide and stir 20~60h, comes into full contact with organic ligand and the titanium dioxide surface hydroxyl in vanadic salts presoma
And replace, then dried after being washed with the solvent, obtain the titanium dioxide solids of vanadium oxygen species modification；Impregnating rule is that will fit
The vanadic salts (one of vanadium trichloride, ammonium metavanadate, sodium metavanadate) of amount is dissolved in ethyl alcohol or water, and (vanadium mass fraction is dense in solution
Degree is 0.1g/L~0.6g/L), it adds solid titanium dioxide and stirs 20~40h, then increase temperature and evaporate solvent, what is obtained consolidates
400~550 DEG C of 2~5h of roasting are warming up to after soma is dry in air, obtain the titanium dioxide of barium oxide modification.
6. according to the method for claim 1, it is characterised in that:
The mass ratio that feeds intake of the catalyst and reaction substrate is 0.1~1.0.
7. according to the method for claim 1, it is characterised in that:
Molar concentration of the substrate in initial reaction system is 0.02~0.15mol/L.
8. according to the method for claim 1, it is characterised in that:
Preferred substrate concentration is 0.05~0.10mol/L；The mass ratio of preferred catalyst and substrate is 20%~80%；
Preferred reaction time is 120~360min；
It is preferred that reaction mixing speed is 300~600r/min；
Preferable reaction temperature is 20~50 DEG C.
9. according to the method for claim 1, it is characterised in that:
The reaction optical source wavelength range is 420~550nm, and preferred wavelength range is 420~480nm.
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| CN111760563A (en) * | 2020-05-20 | 2020-10-13 | 东南大学 | Lignin oxidative depolymerization catalyst and preparation method and application thereof |
| CN113307732A (en) * | 2021-03-30 | 2021-08-27 | 华东师范大学 | Synthetic method of plastic degradation recovery monomer |
| CN113842908A (en) * | 2021-09-27 | 2021-12-28 | 天津理工大学 | Regulation and control of C-C bond aerobic oxidative cracking product by vanadium oxide-based photocatalyst |
| CN114573441A (en) * | 2020-12-02 | 2022-06-03 | 中国科学院大连化学物理研究所 | Method for preparing adipic acid by catalyzing cyclohexene to oxidize |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111760563A (en) * | 2020-05-20 | 2020-10-13 | 东南大学 | Lignin oxidative depolymerization catalyst and preparation method and application thereof |
| CN111760563B (en) * | 2020-05-20 | 2023-08-01 | 东南大学 | Lignin oxidative depolymerization catalyst and preparation method and application thereof |
| CN114573441A (en) * | 2020-12-02 | 2022-06-03 | 中国科学院大连化学物理研究所 | Method for preparing adipic acid by catalyzing cyclohexene to oxidize |
| CN113307732A (en) * | 2021-03-30 | 2021-08-27 | 华东师范大学 | Synthetic method of plastic degradation recovery monomer |
| CN113307732B (en) * | 2021-03-30 | 2022-07-26 | 华东师范大学 | Synthetic method of plastic degradation recovery monomer |
| CN113842908A (en) * | 2021-09-27 | 2021-12-28 | 天津理工大学 | Regulation and control of C-C bond aerobic oxidative cracking product by vanadium oxide-based photocatalyst |
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